Mesomorphic complexes of polyelectrolytes and surfactants, process for producing the same and films, foils, fibers, molded bodies and coatings made thereof

ABSTRACT

Mesomorphic complexes which comprise anionic polyelectrolytes, cationic polyelectrolytes and/or polyampholytes and cationic, anionic, nonionic and/or amphoteric surfactants.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel mesomorphic complexes of anionicpolyelectrolytes, cationic polyelectrolytes and/or polyampholytes andcationic, anionic, nonionic and/or amphoteric surfactants. The inventionfurther relates to methods for preparing them and to films, sheets,fibers, moldings and coatings therefrom.

2. Discussion of the Background

It is known that polyelectrolyte complexes form spontaneously betweenpolyelectrolytes and oppositely charged surfactants. The formation ofcomplexes between polyelectrolytes and nonionic surfactants has likewisebeen described. Most of the relevant publications deal with aqueoussolutions of these complexes, whereas but little is known about theproperties and the structure of such polyelectrolyte-surfactantcomplexes as solids.

EP-A 492 188 (1) describes solid, amorphous complexes ofpolyelectrolytes and oppositely charged surface-active agents which canbe used as sorbents for treating water contaminated with organiccompounds. Herein the complexes are obtained as precipitates by means ofthe polyelectrolyte and the surfactant being mixed in a solvent or bythe polyelectrolyte being prepared in a solution of the surfactant viapolymerization.

DD-A 270 012 (2) describes the preparation of membranes composed of apolyelectrolyte complex comprising cellulose sulfate and a cationicsurfactant The membranes are prepared by a film of cellulose sulfatebeing precipitated with an aqueous solution of the cationic surfactantto produce an amorphous polyelectrolyte complex.

SUMMARY OF THE INVENTION

The materials, such as films or membranes, composed of these amorphouspolyelectrolyte complexes are often still in need of improvement withrespect to their mechanical, thermal or application characteristics. Itis therefore an object of the present invention to provide suchmaterials having improved characteristics.

We have found that this object is achieved by means of the mesomorphiccomplexes of polyelectrolytes and surfactants as defined at the outset.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "mesomorphic" in this context refers to substances or materialswhich have a mesomorphic phase, ie. a liquid-crystalline structure, andin which--at least in certain domains--an ordered arrangement of themolecular building blocks or an ordered arrangement of thesupramolecular aggregates is present. They differ from amorphoussubstances or materials, for example, in that, owing to theiranisotropy, they have special optical properties.

Clearly, in this case, for a number of applications the orientation orordered arrangement of the molecular building blocks and supramolecularaggregates in a mesoscopic or larger dimension is most advantageous. Theorder parameter of the material affects, inter alia, the mechanical,thermal and also the optical properties of the material in question.

The orientation of the molecular building blocks and of thesupramolecular aggregates compared with the corresponding amorphousmaterial, therefore in this case results in an improvement in theapplication properties being achieved or even in the emergence of novel,desirable characteristics.

The mesomorphic structure of the novel polyelectrolyte-surfactantcomplexes can be detected unambiguously by means of small-angle X-raydiffractometry. This shows one or more narrow scattering peaks whichcharacterize a liquid-crystalline morphology. Furthermore, photographsobtained by polarizing microscope under crossed polarizers for themajority of mesomorphic structures indicates typical textures ofbirefringent domain structures.

The novel mesomorphic complexes of polyelectrolytes and surfactantscomprise one polyelectrolyte or a mixture of a plurality ofpolyelectrolytes and one surfactant or a mixture of a plurality ofsurfactants. Said complexes may preferably be composed

of one or more anionic polyelectrolytes and one or more cationic and/ornonionic surf actants or

of one or more cationic polyelectrolytes and one or more anionic and/ornonionic surfactants or

of one or more anionic polyelectrolytes, cationic polyelectrolytesand/or polyampholytes and one or more nonionic surfactants or

of one or more polyampholytes and one or more ionic, amphoteric and/ornonionic surfactants.

The term polyampholytes is to be understood to refer to externallyneutral amphoteric polyelectrolytes.

The anionic polyelectrolytes which are normally used contain from 20 to100 mol % of one or of a mixture of a plurality of the following monomerunit(s) of group (1):

Group (1): monoethylenically unsaturated C₃ - to C₁₀ -monocarboyxlicacids, their alkali metal salts and/or ammonium salts, for exampleacrylic acid, methacrylic acid, dimethylacrylic acid, ethylacrylic acid,allylacetic acid or vinylacetic acid; also monoethylenically unsaturatedC₄ - to C₈ -dicarboxylic acids, their hemiesters, anhydrides, alkalimetal salts and/or ammonium salts, eg. maleic acid, fumaric acid,itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid,maleic anhydride, itaconic anhydride or methylmalonic anhydride; alsosulfo group-containing monoethylenically unsaturated monomers, forexample allylsulfonic acid, styrenesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid,vinylsulfonic acid, 3-sulfopropyl acrylate or 3-sulfopropylmethacrylate; also phosphonic acid group-containing monoethylenicallyunsaturated monomers, eg. vinylphosphonic acid, allylphosphonic acid oracrylamidomethylpropanephosphonic acid.

Said polyelectrolytes can be employed in the acid form, partlyneutralized or completely neutralized. Up to 80 mol % of the monomerunits of the anionic polyelectrolyte in this context may comprise one ormore nonionic monomers of group (2):

Group (2): C₁ - to C₂₀ -alkyl and -hydroxyalkyl esters ofmonoethylenically unsaturated C₃ - to C₁₀ -monocarboxylic acids or C₄ -to C₈ -dicarboxylic acids, eg. methyl acrylate, ethyl acrylate, n-butylacrylate, stearyl acrylate, diethyl maleate, hydroxyethyl acrylate,hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylateor hydroxypropyl methacrylate; also (meth)acrylates of alkoxylated C₁ -to C₁₈ -alcohols which have been reacted with from 2 to 50 mol ofethylene oxide, propylene oxide, butylene oxide or mixtures thereof;also amides and N-substituted amides of monoethylenically unsaturatedC₃ - to C₁₀ -monocarboxylic acids or C₄ - to C₈ -dicarboxylic acids, eg.acrylamide, methacrylamide, N-alkylacrylamides or N,N-dialkylacrylamideseach containing from 1 to 18C atoms in the alkyl group such asN-methylacrylamide, N,N-dimethylacrylamide, N-t-butylacrylamide orN-octadecylacrylamide, maleic acid monomethylhexylamide, maleic acidmonodecyl-amide, dimethylaminopropylmethacrylamide or acrylamidoglycolic acid; also alkylaminoalkyl (meth)acrylates, eg.dimethylamino-ethyl acrylate, dimethylaminoethyl methacrylate,ethylaminoethyl acrylate, diethylaminoethyl methacrylate,dimethylaminopropyl acrylate or dimethylaminopropyl methacrylate; alsovinyl esters, eg. vinyl formate, vinyl acetate or vinyl propionate,where these, after the polymerization, may also be present in saponifiedform; also N-vinyl compounds, eg. N-vinylpyrrolidone,N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide,1-vinylimidazole or 1-vinyl-2-methylimidazole; also vinyl ethers of C₁ -to C₁₈ -alcohols, vinyl ethers of alkoxylated C₁ - to C₁₈ -alcohols andvinyl ethers of polyalkylene oxides such as polyethylene oxide,polypropylene oxide or polybutylene oxide; also linear, branched orcyclic olefins, eg. ethene, propene, butenes, isobutene, 1-pentene,cyclopentene, 1-hexene, 1-heptene, 1-octene, 2,4,4'-trimethylpentene-1,1-nonene, 1-decene, styrene or its derivatives such as α-methylstyrene,indene, dicyclopentadiene or higher olefins carrying reactive doublebonds, such as oligopropene and polyisobutene.

The cationic polyelectrolytes used are normally those carrying aminogroups and/or ammonium groups in the main chain and/or side chain. Toprepare polymers containing amino or ammonium groups it is possible toemploy, eg., the monomers listed in group (3) in proportions of from 20to 100 mol %.

Group (3)

Monomers carrying amino or imino groups, such as eg. dimethylaminoethylacrylate, diethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, allylamine;

monomers carrying quaternary ammonium groups, eg. present as salts suchas are obtained by reacting the basic amino functions with acids such aseg. hydrochloric acid, sulfuric acid, nitric acid, formic acid or aceticacid, or present in quaternized form (suitable quaternizing agentsbeing, for example, dimethyl sulfate, diethyl sulfate, methyl chloride,ethyl chloride or benzyl chloride), such as eg. dimethylaminoethylacrylate hydrochloride, diallyldimethylammonium chloride,dimethylaminoethyl acrylate methochloride,dimethylaminoethylaminopropylmethacrylamide methosulfate,vinylpyridinium salts and 1-vinylimidazolium salts;

monomers in which the amino group and/or ammonium group is un-maskedonly after polymerization and subsequent hydrolysis, such monomers beingeg. N-vinylformamide and N-vinylacetamide.

Other cationic polyelectrolytes which can be used includepolyethyleneimine or polypropyleneimine.

Said polyelectrolytes may be used in the base form, in neutralized formor in completely neutralized form. Up to 80 mol % of the monomer unitsof the cationic polyelectrolyte may then comprise one or more nonionicmonomers of group (2).

Suitable polyampholytes (amphoteric polyelectrolytes) are prepared, as arule, by copolymerization of from 20 to 80 mol % of monomers from group(1) and from group (3), the remaining 0 to 80 mol % optionallycomprising nonionic monomers of group (2).

Suitable anionic surfactants include, for example,alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol polyglycolether sulfates, alkyl glyceryl ether sulfonates, fatty alcoholpolyglycol ether methyl carboxylates, paraffin sulfonates, olefinsulfonates, sulfosuccinic acid hemi- and diesters, alkylphenol ethersulfates and alkyl- and dialkylphosphates. Typical compounds of thistype are, for example, C₈ - to C₁₈ -alkanesulfonates, C₁₂ - to C₁₆-alkyl sulfates, C₁₂ - to C₁₆ -alkyl sulfosuccinates and sulfatedethoxylated C₁₂ - to C₁₆ -alkanols.

Further suitable anionic surfactants include sulfated fatty acidalkanolamines, α-sulfofatty acid esters or fatty acid mono-glycerides.Other suitable anionic surfactants are fatty acid esters or fatty acidsarcosides, fatty acid glycolates, fatty acid lactates, fatty acidtaurides or fatty acid isothionates.

The anionic surfactants may be present in the form of the sodium salts,potassium salts or ammonium salts or as soluble salts of organic basessuch as mono-, di- or triethanolamine or other substituted amines. Theanionic surfactants also include the customary soaps, ie. the alkalimetal salts of the natural fatty acids.

Nonionic surfactants (nonionics) which can be used include, eg.polyalkylene oxide adducts such as ethylene oxide/propylene oxide blockpolymers, fatty acid esters of polyhydroxy compounds, eg. sorbitan alkylesters, glycerol alkyl esters, fatty acid alkylolamides or fatty acidalkylolamido ethoxylates, and addition products of from 3 to 40,preferably from 4 to 20, mol of ethylene oxide to 1 mol of fattyalcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide oralkanesulfonamide. Nonionic surfactants of the type of the amine oxidesor sulfoxides can likewise be used.

The cationic surfactants used are normally those which contain ammoniumgroups, the ammonium compound optionally being based on an open-chainamine, eg. C₈ - to C₁₈ -alkyltrimethylammonium chlorides or bromide,diallyldimethylammonium chloride or lauryl-benzyl-dimethylammoniumchloride. Also suitable are cationic surfactants based on a cyclic amineor imine, eg. cationic surfactants containing pyridinium groups,imidazolinium groups, piperidinium groups, oxazolinium groups orpyrimidinium groups.

Suitable amphoteric surfactants which are externally neutral as a rulecarry basic groups such as amino groups and acidic groups such assulfonate groups, sulfate groups or carboxyl groups. Suitable amphotericsurfactants include, for example, mono- anddialkylaminopropylaminocarboxylic acids and phosphoglycerides.

The preparation of the novel mesomorphic polyelectrolyte-surfactantcomplexes is preferably carried out by a solution of a surfactant,usually in stoichiometric excess with respect to the ionic groups of thepolyelectrolyte, being added to a (partially) neutralized aqueoussolution of the polyelectrolyte which contains ionic groups whose chargeis opposite to that of the surfactant. To dissolve the precipitatedcomplex, which still has an amorphous structure, an organic solvent isadded for the purpose of the present invention, preferably an alcoholwhich is not completely miscible with water, such as 2-butanol, anester, in particular carboxylic acid ester, such as ethyl acetate, anether such as tetrahydrofuran, a ketone such as butanone or a mixture ofsuch solvents in which the complex can redissolve. If required, theorganic phase can be washed a number of times with water, in the senseof a sol-gel separation process, to wash out excess surfactant and salt.Via evaporation of the organic solvent from the solution or gel phaseproduced, the polyelectrolyte-surfactant complex having a mesomorphicstructure is obtained as a solid, eg. as a film. Also present in thesolution or gel phase of the mesomorphic polyelectrolyte-surfactantcomplex may be further components such as polymers or lowmolecular-weight compounds, eg. plasticizers, thickeners, compatibilitypromoters, colorants, light stabilizers, but also structure-stabilizingcomponents such as glass fibers or carbon fibers, which are then alsoincorporated into the resulting solid.

It is further possible for films or layers of the mesomorphicpoly-electrolyte-surfactant complexes to be applied to suitableinorganic or organic substrate materials from the solution or gel phaseproduced by evaporating the organic solvent and thus to for a coatingwith the mesomorphic polyelectrolyte-surfactant complex to be obtained.

To prepare the amorphous polyelectrolyte-surfactant complex as aprecursor in solution it is also possible to add non-neutralizedsurfactants (eg. didodecylmethylamine) to non-neutralizedpolyelectrolytes (eg. poly(acrylic acid)).

The provision of the novel mesomorphic polyelectrolyte-surfactantcomplexes can also be effected without a solvent by them being prepared,for the purposes of the present invention, by processing from the meltof the corresponding amorphous polyelectrolyte-surfactant complexes. Todo this, a melt of an appropriate thermoplastic polyelectrolyte can beadmixed with an appropriate surfactant, or the mixture of an appropriatepolyelectrolyte and an appropriate surfactant can be fused and the meltcan be further processed in a shaping process. via extrusion, forexample, of the molten polyelectrolyte-surfactant complex it is thuspossible to fabricate extrudates, sections, panels, pipes or coatings.Coextrusion, in particular, with further polymers allows the desiredmaterial characteristics to be achieved. Molded parts and sheeting madeof thermoplastic polyelectrolyte-surfactant complexes can be fabricatedby injection-molding or calendering.

Processing from the melt often requires various adjuvants, eg.plasticizers, to be admixed. Additionally, further components such asstabilizers, fillers or colorants may be added to the melt of thepolyelectrolyte-surfactant complex. If required it is also possible formixtures of the polyelectrolse-surfactant complex with further polymersand compatibility promoters to be processed from the melt.

The present invention also relates to industrially useful materials, ie.films, sheets, fibers, molded articles and coatings, the term moldedarticles referrring to, for example, extrudates, sections, panels,pipes, but also granular compositions or pellets, which include thenovel mesomorphic complexes of polyelectrolytes and surfactants or aremade from them.

The content in these materials of the novel mesomorphicpolyelectrolyte-surfactant complexes is usually from 5 to 100 wt. %, inparticular from 50 to 100 wt. %, especially from 80 to 100 wt. %.

The said materials according to the invention are suitable, for example,as materials for producing nonporous membranes, as packaging material(eg. as a barrier film for gases), for producing hollow fibers, as acoating material or as components in optical or electroopticalcomponents.

Owing to the anisotropic properties of the material, the industrialarticles listed exhibit improved mechanical, thermal or applicationcharacteristics, compared with the corresponding conventional industrialarticles; for example, these materials can be used to produceoxygen-impermeable films which can advantageously be used for packaginghighly perishable food.

Preparation and characterization examples

EXAMPLE 1

Preparation of polystyrene sulfonate sodium salt (PSSNa)

Anionically polymerized polystyrene (M_(w) =449,000 g/mol, M_(w) /M_(n)<1.05) was converted by means of sulfuric acid and phosphorus pentoxide,by a method similar to the method by H. Vink, into the sodium salt ofpolystyrene sulfonic acid (H. Vink, Makromol. Chem. 182, 279, 1981). Thedegree of sulfonation S was determined by elemental analysis and wasS>0.9. The polystyrene sulfonate sodium salt was dialyzed againstdeionized water and freeze-dried.

EXAMPLES 2 TO 5

Preparation of the complex of PSSNa and alkyltrimethylammonium chloride

PSSNa (5.0 g) was dissolved in 0.01 molar aqueous sodium sulfatesolution (400 ml). A 1.5-fold stoichiometric excess ofdodecyltrimethylammonium chloride (9.6 g), dissolved in deionized water(100 ml), was added dropwise. The precipitated complex was filtered offand washed with water.

The dodecyltrimethylasmonium chloride (Example 2) was replaced by 10.6 gof tetradecyltrimethylammonium chloride (Example 3), 11.6 g ofhexadecyltrimethylammonium chloride (Example 4) and 12.7 g ofoctadecyltrimethylammonium chloride (Example 5). The reactions andworkup were carried out by a method similar to Example 2.

EXAMPLES 6 TO 9

Purification of the PSSNa-alkyltrimethylammonium chloride complexes fromExamples 2 to 5

The precipitated complex which still contained certain amounts of excesssurfactant and of resulting salt was dissolved in 2-butanol. Deionizedwater was added until phase separation into a complex-rich gel phase anda surfactant- and salt-rich aqueous phase occurred. The aqueous phasewas discarded and the sol-gel separation process was repeated a numberof times until the water phase was virtually free from halide ions(detection by means of AgNO₃).

EXAMPLES 10 TO 13

Preparation of mesomorphic films from the purifiedPSSNa-alkyltrimethylammonium chloride complexes of Examples 6 to 9

The gel phase of the complex in 2-butanol was poured onto a planar glassplate which had been pretreated with octadecyltrichlorosilane. In sodoing, the two-dimensional geometry of the film being formed waspredefined by an adjustable sheet metal frame which was mounted on theglass surface. After the solvent 2-butanol had slowly evaporated, thefilm could be easily peeled off the glass surface.

EXAMPLES 14 TO 17

Measurement of the small-angle X-ray diffractograms of the mesomorphicfilms from Examples 10 to 13

The small-angle X-ray diffractograms were measured by means of an AntonPaar compact Kratky camera using a Cu-K.sub.α source (Phillips pw1830generator). Monochromatization was performed by means of a nickelfilter. Pulse height discrimination was applied. The measurements werecarried out in a scattering-vector range of from 1.0·10⁻³ Å⁻¹ to9.0·10⁻² Å⁻¹. The scattering vector s is defined by s=2/λ·sinθ, 2θdenoting the angle between the incident ray and the scattered ray, and λsignifying the wavelength of the radiation used.

The table following Example 21 shows the results of the measurements onthe films from Examples 10 to 13.

EXAMPLE 18

Preparation of a complex of poly(acrylic acid) anddodecyltrimethylammonium chloride

Poly(acrylic acid) (5.0 g, M_(w) =250,000 g/mol) was dissolved in waterand converted into the sodium salt by means of NaOH. A solution ofdodecyltrimethylamonium chloride (24 g) in water (200 ml) was addeddropwise with stirring. The precipitated complex was filtered off.

EXAMPLE 19

Purification of the complex from Example 18

The purification was carried out by a method similar to that indicatedin Examples 6 to 9.

EXAMPLE 20

Preparation of a mesomorphic film from the purified complex from Example19

The mesomorphic film was prepared by a method similar to that indicatedin Examples 10 to 13.

EXAMPLE 21

Measurement of the small-angle X-ray diffractograms of the mesomorphicfilm from Example 20

The measurement was carried out in accordance with the method specifiedin Examples 14 to 17. The following table shows the measurement on thefilm from Example 20.

                  TABLE    ______________________________________    Small-angle X-ray diffractograms (position of the main peak)    Example No.      I/cps  s/nm.sup.-1    ______________________________________    14               98     0.34    15               93     0.32    16               88     0.285    17               260    0.245    21               305    0.30    ______________________________________

We claim:
 1. A mesomorphic complex of an anionic polyelectrolyte,cationic polyelectrolyte and/or polyampholyte and a cationic, anionic,nonionic and/or amphoteric surfactant, said complex comprising(a) one ormore anionic polyelectrolytes and one or more cationic surfactants or(b) one or more cationic polyelectrolytes and one or more anionicsurfactants or (d) one or more polyampholytes and one of more ionic,amphoteric and/or nonionic surfactants.
 2. A method for preparing amesomorphic complex of a polyelectrolyte and surfactant as claimed inclaim 1, which comprises dissolving a corresponding amorphouspolyelectrolyte-surfactant complex, a stoichiometric excess of saidsurfactant with respect to the ionic groups of the polyelectrolytehaving been used to prepare them, in an organic solvent and evaporatingsaid solvent from a solution or gel phase produced.
 3. A method forpreparing a mesomorphic complex of a polyelectrolyte and surfactant asclaimed in claim 1, which comprises preparing said complex by processingfrom a melt of a corresponding amorphous polyelectrolyte-surfactantcomplexes.
 4. A film, sheet, fiber, molding or coating containing themesomorphic complex of a polyelectrolyte and surfactant as claimed inclaim
 1. 5. A method for preparing a mesomorphic complex of apolyelectrolyte and a surfactant, which comprises preparing said complexby processing from a melt of a corresponding amorphouspolyelectrolyte-surfactant complexes, wherein said complex comprises(a)one of more anionic polyelectrolytes and one or more cationic and/ornonionic surfactants or (b) one of more cationic polyelectrolytes andone or more anionic and/or nonionic surfactants or (c) one or moreanionic polyelectrolytes, cationic polyelectrolytes and/orpolyampholytes and one or more nonionic surfactants or (d) one or morepolyampholytes and one or more ionic, amphoteric and/or nonionicsurfactants.
 6. A film, sheet, fiber, molding or coating containing 50to 100 wt. % of a mesomorphic complex of a polyelectrolyte and asurfactant, wherein said complex comprises(a) one of more anionicpolyelectrolytes and one or more cationic and/or nonionic surfactants or(b) one of more cationic polyelectrolytes and one or more anionic and/ornonionic surfactants or (c) one or more anionic polyelectrolytes,cationic polyelectrolytes and/or polyampholytes and one or more nonionicsurfactants or (d) one or more polyampholytes and one or more ionic,amphoteric and/or nonionic surfactants.
 7. The film, sheet fiber,molding or coating of claim 6, wherein the mesomorphic complex isprepared by a process comprising dissolving a corresponding amorphouspolyelectrolyte-surfactant complex, a stoichiometric excess of saidsurfactant with respect to the ionic groups of the polyelectrolytehaving been used to prepare them, in an organic solvent and evaporatingsaid solvent from a solution or gel phase produced.
 8. The film, sheet,fiber, molding or coating of claim 6, wherein the mesomorphic complex isprepared by processing from a melt a corresponding amorphouspolyelectrolyte-surfactant complex.
 9. A film, sheet, fiber, molding orcoating containing 5 to 100 wt. % of the mesomorphic complex of claim 1.10. A film, sheet, fiber, molding or coating containing 50 to 100 wt. %of the mesomorphic complex of claim
 1. 11. A film, sheet, fiber, moldingor coating containing 80 to 100 wt. % of the mesomorphic complex ofclaim
 1. 12. The film, sheet, fiber, molding or coating of claim 6,containing 80 to 100 wt. % of the mesomorphic complex.
 13. Themesomorphic complex of claim 1, said complex comprising one or moreanionic polyelectrolytes.
 14. The mesomorphic complex of claim 1, saidcomplex comprising one or more cationic polyelectrolytes.
 15. Themesomorphic complex of claim 1, said complex comprising one or morepolyamopholytes.
 16. The film, sheet, fiber, molding or coating of claim6, said mesomorphic complex comprising one or more anionicpolyelectrolytes.
 17. The film, sheet, fiber, molding or coating ofclaim 6, said mesomorphic complex comprising one or more cationicpolyelectrolytes.
 18. The film, sheet, fiber, molding or coating ofclaim 6, said mesomorphic complex comprising one or more nonionicsurfactants.
 19. The film, sheet, fiber, molding or coating of claim 6,said mesomorphic complex comprising one or more polyamopholytes.